Poly(vinyl acetate) (PVA) prepared by photopolymerization was studied by a combination of one and two dimensional NMR spectroscopy. The C-13{H-1} and H-1 NMR spectra of the homopolymer (PVA) were assigned to the configurational pentads (CH region) and tetrads (CH2 region). These assignments were substantiated by the use of two dimensional heteronuclear single quantum correlation (HSQC), heteronuclear single quantum correlation-total correlation spectroscopy (HSQC-TOCSY) and double quantum filtered correlation spectroscopy (DQFCOSY) experiments. The results obtained by the analysis of the area under the resonance signals confirmed that PVA obeys Bernoullian statistics.